Cellulose ethers and esters plasticized with a di-(chloro-butoxybutyl) phthalate



Patented Oct. 17, 1950 UNITED STATES PATENTOFFICE CELLULOSE ETHERS AND ESTERS PLASTI- CIZED WITH A DL-(CKLORO-BUTOXY- BUTYL) PHTHALATE Gershon J. Shugar, Jersey City, N. 1., assignor to Celanese Corporation of America, a corporation of Delaware No Drawing. Application June 11, 1941, Serial No. 154,052

6 Claims. (Cl. 106-179) I have now found that the chlorobutyl as well asthe chloro-butoxy butyl esters of various organic acids of the'following generali'ormula:

wherein n is a whole number not greater than 2,

X is hydrogen or and R is a member of the group consisting of alkylene and arylene radicals, are excellent solvent and plasticizing agents for certain synthetic resins as well as for cellulose acetate or other cellulose derivative materials.

These esters may be obtained in excellent yield by catalyticaliy reacting tetram'ethylene oxide under refluxing temperature with the acid chloride of the corresponding monobasic and'polybasic organic acid whose chlorobutyl or chlorobutoxy butyl ester is desired. The reaction effectively opens the tetra-methylene oxide ring and causes a molecular rearrangement whereby chlorobutyl and chlorobutoxy butyl esters of the organic acid are formed. Preferably, I employ a catalyst such I as anhydrous zinc chloride, aluminum chloride, concentrated sulfuric acid or concentrated phosphoric acid to aid the reaction. The catalysts employed may be present in an amount of from 0.5 to 5.0% by weight on the tetramethylene oxide undergoing reaction.

Thus, by reacting tetramethylene oxide at reflux temperature with the acid chlorides of monobasic and 'polybasic organic acids, suchas, for example, phthalyl dichloride, stearyl chloride, heptoic acid chloride, caproyl chloride, capric acid chloride, lauroyl chloride, sucwinyl di -chloride, adipyl di-chloride or sebasic acid di-chloride, the corresponding chlorobutyl and chlorobutoxy butyl esters of these acids are obtained.

In forming the novel plasticized compositions of my invention, the chlorobutyl and chlorobutoxy butyl esters may be incorporated in the thermoplastic cellulose derivative or other compounds being plasticized in amounts of from about 5 to '15 parts or more by weight for each 100 parts by weight of cellulose derivative or other plasticizabie compound present. When forming plasticized compositions which are'to be, employed in molding operations, the plasticizer may he placed on the thermoplastic compound with or without the aid of a volatile solvent in which it may be dissolved, to assist in uniformly distributing the plasticizer. A Banbury mixer may be used to mix the plasticizer with the resin or cellulose derivative. If a solvent is employed. the latter may then be evaporated, the composition thoroughly mixed or compounded with pigments or other effect materials on hot mixing rolls, for example,

and after rolling the uniformly mixed composition out into thin sheets and cooling the same. the sheetsmay then be broken up into the form of a molding powder. In forming plasticized films and foils. the desired amount of plasticizer and cellulose derivative base material or other plasticizable base material being employed are usually dissolved in a volatile solvent or mixture of volatile solvents and the resulting dope or solution cast into illms or foils on a suitable surface as, for example, a rotating drum or wheel. The volatile solvent evaporates leaving a film or foil of the eellulose derivative base material which may then be stripped from the surface upon which it is formed and taken up in roll or other form.

As examples of organic derivatives of cellulo-e Y which may be plasticized with said chlorobutyl esters there may be mentioned cellulose esters such as cellulose nitrate, cellulose acetate, cellulose propionate. cellulose butyrate', cellulose acetatepropionate, and cellulose acetate-butyrate as well as cellulo e ethers' such as ethyl cellulose and benzyl cellulose.

As examples of polyvinyl compounds with which the chlorobutyl organic acid esters are compatible there may be mentioned polyvinyl chloride. polyvinyl acetate as well as copolymers of polyvinyl chloride and polyvinyl acetate. The chlorobutyl and chlorobutoxy butyl esters are also compatible with alkyd resins such asglyceryl phthalate, coumaron-indene resin and methyl methacrylate.

In order further to illustrate my invention, but without being limited thereto, the following examples are given:

Example I 830 parts by weight of tetramethylene oxide and 0.1 part by weight of freshly fused zinc chlo ride are placed in a reaction vessel and 453 parts by weight of acetyl chloride are gradually added thereto. The resulting reaction is exothermic and as the temperature of the reaction mixture rises refluxing commences at about 73 C. At the completion of the addition of the temperature a,sae,oe1 3 4 rises to about 84 C. and the reaction mixture is rine content lends increased ilre retarding-action then refluxed for about two hours. Completion tothe plasticized films, as compared to films pinsof the reaction is determined by diluting about ticized with dibutyl phthalate, 10. cos. oi the reaction mixture with 90 cos. of distilled water and observing the amount of wa- Example ter-insoluble product obtained. The greater the 5 100 parts by weight of ethyl cellulose (45 to amount of water-insoluble product the more 47% ethoxyl) are mixed with 20 parts by weight nearly complete is the reaction. When no 'inof di-chlorobutyl-phthalate and 1 part by weight crease in water-insolubles is noted on dilution. of calcium lactate which acts as a stabilizer. The after the reaction is continued further, the reacplasticized ethyl cellulose is then molded into tion product is then fractionally distilled. A discs at a temperature of 200' c. for minutes.

) yield of about 80% of theoretical of chlorobutyl The discs obtained are clear, practically coloracetate is obtained boiling at 90" C. at mm. less and possess good impact strength and surface pressure. A yield of 10% of chlorobutoxy-butylhardness.

acetate is obtained also. This compound boils at It i to b understood that th foregoin dc;

168 C. at 31 mm. pressure. Chlorobutyl acetate t il d degcflptiofl i given merely by way of 11 possesses solvent action on cellulose nitrate, celnation and that many MMom my be made lulose acetate, cellulose propionate, ethyl cellutherein without departing from the spirit of my lose, polyvinyl chloride, alkyd resins, such as glyinvention ceryl phthalate, coumaron-indene resin and Having m 1 can methyl methacrylate. It is also found to be misto secure g i rg z az j what I d cible with pentane and castor oil and many plas- L A composition of matte; comprising an op ticizers. The second compound i. e. chlorobuganic derivative of cellulose, selected from the zfg gi possesses the same solvent group consisting of cellulose esters and cellulose Example H ethers, plasticized with an ester of an organic acid having a plasticizing action thereon of the 100 parts by weight of tetramethylene oxide following formula are added dropwise to a reaction vessel contain- 2. A composition of matter comprising celluing 430 parts by weight of stearyl chloride which lose acetate plasticized with an ester of an organhas been heated to about 170 C. As the ringic acid having a plasticizing action thereon oi opening and esteriflcation reaction proceeds, the the following formula temperature rises to about 200 C. The reaction 3. A composition of matter comprising ethyl mixture is refluxed at 200 C. for 8 hours to encellulose plasticized with an ester of an organic sure com letion of the reaction. After reac ion acid having a plasticizing action thereon of the is complete, the reaction mixture is then fracfollowing formula I o o ck(CHQCHlCHIdHi-O)P-Ph0fl1kfl(0CHQCHICH1CHQR-Cl tionally d st lled under reduced ressure. The 4. A composition of matter comprising celluchlorobutyl-stearate formed is a li ht ye'low oil lose acetate plasticized with di-(chlorobutoxy buwhich boils at 255 to 260 C. at 15 mm. pressure, tyD-phthaIate,

has a dens ty of 0.923 at 25 C. and a. refractive 5,- A composition f matter comprising ethyl index of 1.45i5 at 25 C. When heated, th s ester cellulose plasticized t 41. (chlorobutoxy butyl) is found to be compatible. for exam le, with celm m lulose nitrate cellulose ester 6. A composition of matter comprising cellumaron'indene resin? methyl methacrylate' lose propionate pla'sticized with di-(chlorobutoxy Example III YD-Phthalate.

G ON J. SHU AR. 144 parts by weieht of etr methylene oxide ERSH G are added dropwise into a suitable reaction vessel REFERENCES CITED conta ning 203 parts by we ht of phthalyl di- A o The following references are of record in the chloride heated to about 200 C. The reaction me of this patent:

mixture is then refluxed for 4 hours at about 200 c. The unreaoted phthalyl dichloride is removed UNITED B' 'A' S PATENTS by washing the reaction mixture with a 10% Numwer Name Date aqueous ium carbonate solution. 0n frac- 10,879 Amend Nov. 8, 1887 ti nal d stillation. a fraction compris ng di-chlo- 1,027,615 Lindsay May 28, 1912 ro yl-ph halate boiling at 230 to 240 c. under 66 1339315 Kessler Dec 10' 1929 3 Pressure 18 b ined. This compound has 1 82 91 nn Oct 6 1931 a density of at 25 C. and a refractive index 1 94 43 Smith Feb. 13' 1934 of 1.5175 at 25 C. When heated it dissolves cel- 1,949,093 yam schaack 27, 1934 lulose nitrate, cellulose acetate, cellulose propion- 2,062,403 Dreyfus et aL 1' 1936 ethyl celluloseester 8 1 glyceryl phthalate. 1o 2 202 01 t May 28, 1940 methyl methacrylate, etc. Films of cellulose proprionate of 0.3 free hydroxyl groups contain- FOREIGN PATENTS ing 20 and 30 parts by weight of di-chlorobutyl- Number Country Date phthalate for each parts by weight of the cel- 374,322 Apr. 21, 1923 lulose propionate are clear and tough. The chlO- 16 r Certificate of Correction Patent No. 2,525,961 October 17, 1950 GERSHON J. SHUGAR It is hereby certified that error appears in the printed specification of the above numbered patent requiring correction as follows:

Column 1, lines 7, 12 and 13, for the word organic read phthalz'c; column 2, line 60, strike out of after addition;

and that the said Letters Patent should be read as corrected above, so that the same may conform to the record of the case in the Patent Oflice.

Signed and sealed this 26th day of December, A. D. 1950.

THOMAS F. MURPHY,

Assistant Gommissioner of Patents. 

1. A COMPOSITION OF MATTER COMPRISING AN ORGANIC DERIVATIVE OF CELLULOSE, SELECTED FROM THE GROUP CONSISTING OF CELLULOSE ESTERS AND CELLULOSE ETHERS, PLASTICIZED WITH AN ESTER OF AN ORGANIC ACID HAVING A PLASTICIZING ACITON THEREON OF THE FOLLOWING FORMULA 